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Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films

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Abstract

The initial steps of the thermal chemistry of Cu(I)-2-(tert-butylimino)-5,5-dimethyl-pyrrolidinate on metal surfaces were characterized using temperature-programmed desorption experiments and density functional theory (DFT). The relative stability of the initial dimer relative to its dissociation on metal surfaces was evaluated. Several molecular desorption temperatures were identified on Ni(110), but all correspond to dimers, either containing the initial Cu ions or after their removal; no monomer was ever detected. DFT calculations also indicated preferential bonding on Cu(110) as a dimer, albeit with a distorted configuration, via the Cu atoms and in registry with the lattice of the substrate. A potential dissociation pathway of the adsorbed dimer was identified involving the partial detachment of the ligands via the scission of one Cu–N bond at the time and migration to adjacent surface sites. This process is accompanied by the reduction of the Cu centers of the metal–organic complex, indicating that it may be the rate-limiting reaction that leads to further fragmentation of the ligands.

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Acknowledgments

Financial support for this project was provided by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering (MSE) Division, under Award No. DE-SC0001839. N.T. and J.G.S. thank DGAPA-UNAM Project IN100516, and Conacyt Grant A1-S-9070 of the Call of Proposals for Basic Scientific Research 2017–2018 for partial financial support. N.T. thanks DGAPA-UNAM for a scholarship at the University of California, Riverside. Calculations were performed in the DGCTIC-UNAM Supercomputing Center, project LANCAD-UNAM-DGTIC-051.

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Authors and Affiliations

  1. Centro de Nanociencias y Nanotecnología, Universidad Nacional Autónoma de México, Ensenada, Baja California, 22800, México

    Jonathan Guerrero-Sánchez & Noboru Takeuchi

  2. Department of Chemistry, University of California, Riverside, California, 92521, USA

    Bo Chen, Noboru Takeuchi & Francisco Zaera

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  1. Jonathan Guerrero-Sánchez
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Correspondence to Francisco Zaera.

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Guerrero-Sánchez, J., Chen, B., Takeuchi, N. et al. Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films. Journal of Materials Research 35, 720–731 (2020). https://doi.org/10.1557/jmr.2019.293

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